2881
and affords the hemiketal 5 in nearly quantitative yield. HO OCH, 0
K
II
Treatment of 2 with dry HC1 leads to the unexpected result that the two isomeric a-chloro ketones l l a and l l b are produced in the rate 40 :60 (-60 % over-all yield). 0
II
(3)
I cH3
T
I
0
I
(CHJrC=C=0
I
5
CH3
0
25'
llb
1l a
Attempts to collect 2 by preparative vpc lead to formation of methyl isopropenyl ketone (12).
6
7
8
Treatment of 2 with excess diazomethane (eq 4) affords the cyclobutanones 6 and 7 in the ratio 25:75, confirming earlier predictions that cyclopropanones are enormously more reactive than cyclobutanones in an uncatalyzed ring expansion with diazomethane. 14-17 Compound 2 reacts with dimethylketene at room temperature to yield the novel cycloadduct 8 (eq 5 ) . Compound 8 possesses the following properties: mass spectrum, mje 154 (molecular ion, 1.1 %), 110 (loss of C02, 9 . 5 7 3 , 70 ((CHs)ZC=C+=O, loo%), 56 ((CH3)y 5.47 p ; nmr AB C+=CH2, 20%); infrared, quartet centered at 0.67 ppm (J = 7 cps), four threeproton singlets at 1.38, 1.29, 1.25, and 1.10 ppm. The reaction of cyclopropanones with I,3-dienes is predicted to occur in a concerted manner to yield 1,4-1,3 adducts.'* The addition of 2 and 2-methylfuran yields a mixture of the 1,4-1,3 adducts 9 and 10 in the ratio 58 : 42, a result not inconsistent with a concerted mode of addition. 2
+
fyH3 9
12
Cyclopropanone itself is available from the reactions of diazomethane and ketene. 1 5 ~ 1 7 , 1 3 The preparation and reactions of other cyclopropanones is under vigorous study in our laboratory. Acknowledgments. The authors are indebted to the National Science Foundation (Grant NSF-GP-4280) and the Air Force Office of Scientific Research (Grant AFOSR-1000-66) for their generous support of this work. (19) W. B. Hammond and N. J. Turro, unpublished results. The greater ease of handling 2 compared to 1 encourages us to feel that cyclopropanone itself may be a tractable organic compound. (20) National Science Foundation Predoctoral Fellow, 1964-1966. (21) Fellow of the Alfred P. Sloan Foundation.
Willis B. Hammond,20Nicholas J. Turro21 Department of Chemistry, Columbia University New York, New York 10027 Received April 22, 1966
The Photochemical 1,3 Addition of Alcohols to Benzenes'
10
Compounds 9 and 10 were shown to be isomeric by mass spectrometry (molecular ion, m/e I66 common to both); infrared of both compounds possesses A=: 1720 cm-l; nmr of 9 shows a simple AB quartet centered at 2.35 ppm (J = 15 cps) while 10 shows an ABX spectrum, the AB portion centered at 2.40 ppm, X centered at 4.85 ppm (J*B = 15.2 cps, J u = 4.7 cps, J B X = 1.3 cps). (13) Compound 5 possesses molecular weight of 116 (mass spectrum) and its nmr shows an AB quartet centered at 0.58 ppm, J = 5 cps. (14) J.-M. Conia and J. Salaun, Bull. Chem. Soc. Fronce, 1957 (1964); M. D.Owen, G. R. Ramage, and J. E. Simonsen, J. Chem. Soc., 1213 (1938). (15) P. Lipp and R. Koster, Eer., 64,2823 (1931). (16) D.A. Semenow, E. F. Cox, and J. D. Roberts,J. Am. Chem. Soc., 78. 3221 (1956). (17) A.' S. Kende, Ph.D. Dissertation, Harvard University, 1956. (18) R. Hoffmann and R. B. Woodward, J. Am. Chem. Soc., 87. 4388 (1965).
Sir : We wish to report a new photochemical reaction, the formation of alkoxy[3.1.O]bicyclohexenes by I ,3 addition of alcohols to benzene and alkylbenzenes. In the case of 1,3,5-tri-t-butylbenzene,the quantum yield for this addition reaction in methanol is severalfold greater than that for the isomerization observed2 in hydrocarbon solutions. Furthermore, the bicyclic ether is formed to the exclusion of the isomeric hydrocarbons. The structure of the product (I) suggests that it is formed by addition3 of methanol to 1,2,4-tri-t-butylbenzvalene4 (11) or an excited state closely resembling it. It is reasonable to conclude that the same intermediate is formed in hydrocarbon solvents and is the precursor (1) Based on work performed under the auspices of the U. S. Atomic Energy Commission. (2) K. E. Wilzbach and L. Kaplan, J . Am. Chem. Soc., 87, 4004
(I 965). (3) Related photochemical additions of alcohols to conjugated dienes are discussed by W. G. Dauben and W. T. Wipke, "Organic Photochemistry," Butterworths, London, 1965,p 539. (4) Following the suggestion of J. Meinwald and J. K. Crandall, J. Am. Chem. Soc., 88, 1292 (1966), we are renaming benzvalene as tricyclo[3.1.0.0*~~]hex-3-ene to accord with IUPAC rules. Compound III was previously' called 2,5,6-tri-t-butyltricyclo[2.l.0.0~~~]hex-2-ene.
Communications to the Editor
2882
I
II
m
of the 1,3,6-tri-t-b~tylbenzvalene~~~ (111) and 1,2,4tri-t-butylbenzene isomers. The lower quantum yields observed in the hydrocarbon solutions indicate that the intermediate returns in large part to 1,3,5-tri-t-butylbenzene. Although benzene does not appear to react in this manner with methanol, it does yield two adducts (IV and V) upon photolysis in trifluoroethanol.6 The nature of these products suggests that the reaction follows a similar course.
H ISL Irradiation of 1,3,5-tri-t-butylbenzenein methanol solution (-0.02 M ) at 2537 A (4-w Germicidal lamp, Corning 7910 filter) and room temperature results in its disappearance with a quantum yield of 0.15. The only product detectable by nmr, either initially or after 90% conversion, is the adduct I, a white solid, mp 35”, recrystallizable from methanol. It has been character.O]bicyclohex-2ized as 4-methoxy-2,4,6-tri-t-butyl[3.1 ene (I) on the basis of the following properties: the ultraviolet spectrum shows only end absorption above 2000 A (tzzoo 2500). The nmr spectrum7 exhibits singlets of 9 H (t-butyl) at T 8.87,9.04, and 9.10 and of 3 H (OCH,) at T 7.02 and multiplets of 1 H at T 5.24, 8.31, 8.86, and 9.27. The latter can be assigned* to positions 3, 5, 1, and 6 (endo), respectively, on the basis of their chemical shifts and coupling constants (JIJ= 1.5, J I , ~= 5.7, J1,6= 4.6, and J 5 , g = 2.7 cps). Both the stereochemistry of the proton at C-6 and the absence of this resonance in the adduct from CH,OD are consistent with addition to a benzvalene-like structure. Photolysis of benzene in trifluoroethanol under similar conditions yields as the principal products IV and V in a ratio of about 2 : 1 (+total = 0.05). They are readily isolated by gas chromatography (retentions relative to mesitylene on QF1 at 50”: V = 0.95, IV = 1.38). Their ultraviolet absorptions are similar: no maximum above 2000 A (€2200 -3000). The infrared spectrum of IV shows strong C-H vibrations at 3.27 and 3.41 p and a double bond vibration at 6.27 ( 5 ) Since solutions of I11 in methanol are stable at room temperature and photolyze predominantly to 1,2,4-tri-t-butylbenzene,it may be concluded that I11 is not formed during the photolysis of 1,3,5-tri-tbutylbenzene in this solvent. (6) Two products, not yet fully characterized, are also formed from 1,3,5-trl-t-butylbenzenein this solvent. (7) 100-Mc spectra taken in cc14 solution with a Varian HA-100 spectrometer. We thank Miss Gail Norman for these spectra. (8) The spectral data are also consistent with an isomer in which the t-butyl group is at C-3 instead of C-2. Thermal decomposition of the adduct at 200” to 1,3,6-tri-t-butylfulvene provides evidence that the tbutyl groups are not on adjacent carbon atoms. Characterization of this fulvene will be reported later.
p ; the corresponding values for V are 3.28, 3.43, and 6.22 p. The nmr spectrum of IV shows multiplets of one proton each centered at T 3.71, 4.58, 5.55, -8.1, -8.3, 9.06, and 10.10 and a quartet of two protons (OCHEF,) at T 6.13. The appearance of only two olefinic protons, coupled with 5.5 cps, and of the two high-field protons (gem-cyclopropyl, J = 4 cps) leads to the conclusion that the product is 4-trifluoroethoxy[3.l.O]bicyclohex-2-ene. The nmr spectrum of V consists of multiplets of one proton each centered at r 4.41, 4.53, 8.03, and 8.26, two nonidentical protons at T 7.5, and a proton at T 6.5 partially obscured by the characteristic quartet of the OCHzCF3 protons centered at r 6.46. As with IV, there are only two olefinic protons, coupled with 5.6 cps, indicating that this compound is also a bicyclohexenyl ether. The absence of the high-field protons suggests that the alkoxy1 group is on the cyclopropane ring. By double resonance, the proton at r 6.5 is shown to be strongly coupled ( J - 7 cps) to each of the r 8 bridgehead protons and is therefore in the exo position on the cyclopropane ring. The conclusion that V is 6-endo-trifluoroethoxybicyclo[3.1.0]hex-2-ene is further supported by the similarity in nmr spectrum with those of the methyl and hexyl ethers reportedg by Schollkopf and Paust. The stereochemistry of V is again that which would be expected from addition to a benzvalene-like structure. The alcohol additions reported here bear at least a superficial resemblance to the previously reported lo additions of olefins to benzene. The relationship between these reactions and the nature of the intermediates is under investigation.*O” (9) U. Schollkopf and J. Paust, Ber., 98, 2221 (1965); U. Schollkopf, personal communication. (10) K. E. Wilzbach and L. Kaplan, J . Am. Chem. SOC.,88, 2066 (1966). (loa) NOTEADDEDIN PROOF. Methoxy derivatives analogous to Iv and V are formed by irradiation of benzene in methanol containing a trace of hydrochloric acid. (1 1) Student Aide, A.C.M. Argonne Semester Program.
Louis Kaplan, James S. Ritscher,” K. E. Wilzbach Chemistry Diuision, Argorine Nutioriul Laboratory Argontze, Illinois Received April 15, 1966
The Photoisomerization of Dibenzobicyclo[2.2.2]octatrienes Sir: Recently, Zimmerman and Grunewald reported the photoisomerization of bicyclo[2.2.2]octa-2,5,7-triene (“barrelene”) to tricyclo[3.3.0.02~*]octa-3,6-diene (“semibullvalene”). We have independently observed this rearrangement in the photolysis of a number of dibenzobicyclo[2.2.2]octatrienes. Irradiation of an acetone solution of dibenzobicyclo[2.2.2]octatriene (la)2 with a Philips HPK 125 highpressure mercury lamp (Pyrex filter) gave dibenzotricyclo[3.3.0.02~*]octadiene(2a) in 85 % yield. The nmr spectrum of this product was identical with that reported for 2a obtained by dimerization of benzocyclobutadiene. Further structure proof was ob-
Journal of the American Chemical Society / 88:12 / June 20, 1966
(1) H. E. Zimmerman and G. L. Grunewald, J . A m . Chem. SOC.,88, 183 (1966). (2) S. J.CristolandR.I
